FIELD OF THE INVENTION

[0001] The invention relates to dimeric cyanoacrylate compounds linked through either the ester alkyl group (Type I) or the p-hydroxy group (Type II), useful as red- shifted UV absorbers having low volatility, compositions thereof, and methods for using same.

BACKGROUND OF THE INVENTION

[0002] Many natural and synthetic polymers are attacked by ultra-violet radiation and products made using these materials, as well as the contents of packaged items, may spoil, crack, or disintegrate. Many pigments and dyes can also be affected, when the problem is known as photo tendering in textiles such as curtains or drapes. The problem is known as UV degradation, and is a common problem in products exposed to sunlight. The UV-A region of the electromagnetic spectrum encompasses wavelengths between 320 nm to 400 nm. It has become increasingly apparent that radiation in this region contributes to the degradation of polymers, which in turn has deleterious effects on the content housed by such polymers. Continuous exposure is a more serious problem than intermittent exposure, since attack is dependent on the extent and degree of exposure. UV attack by sunlight can be ameliorated or prevented by adding anti-UV chemicals to the polymer when mixing the ingredients, or prior to shaping the product by injection moulding for example. Numerous UV stabilizers for preventing or minimizing UV degradation are known in the art.

[0003] As UV radiation is responsible for the degradation of polymer products and the contents contained within such packaging, there is a market need for UV absorbers that have absorption maxima in the mid- to high UV-A region. While there are some commercial products that attempt to accomplish this (e.g., Clearshield® from Milliken), they suffer from certain deficiencies, including thermal volatility and solubility/compatibility issues. [0004] Accordingly, UV absorber compounds that have good absorbance in the mid- to high UV-A region of the electromagnetic spectrum and having good volatility and solubility/compatibility with common solvents, and with polymers into which they are incorporated, are desirable.

SUMMARY OF THE INVENTION [0005] It has now been discovered that certain dimeric cyanoacrylates are useful as red-shifted UV absorbers demonstrating absorbance in the 350 nm and up range, and that these compounds possess low volatility and are more compatible with common solvents and polymers than previously described materials. [0006] In one aspect, the invention provides dimeric cyanoacrylate compounds of

Formula (I) or Formula (II)

wherein

R ¹ and R ² are independently chosen from hydrogen, C ₁ -C _3O alkyl, and -(CH ₂ ) _q -C(O)-OR ⁹ , wherein R ⁹ is chosen from hydrogen and C ₁ -C _3O alkyl optionally interrupted with oxygen, provided no oxygen atom is adjacent to another, and wherein q is an integer from 1 to 20;

R ³ and R ⁴ are independently chosen from hydrogen and C ₁ -C ₆ alkoxy; R ⁵ and R ⁶ are independently chosen from C ₁ -C _3O alkyl, and

-(CH ₂ CH ₂ θ) _m -(CH ₂ ) _n -CH ₃ , wherein m is an integer from 1 to 20, and n is an integer from 0 to 20;

R ⁷ and R ⁸ are independently chosen from R ³ and R ⁴ ; and

X ¹ and X ² are independently chosen from C ₂ -C _3O alkylene and

-( CH ₂ CH ₂ O) _P -CH ₂ CH ₂ -, wherein p is an integer from 1 to 20. [0007] In a second aspect, compositions having two or more dimeric cyanoacrylate compounds are provided. [0008] In a third aspect, compositions having one or more dimeric cyanoacrylate and a UV stabilizer are provided. [0009] In a fourth aspect, methods of stabilizing a material that is subject to degradation by UV radiation by incorporating one of the compounds or compositions disclosed herein are provided. [0010] These, and other objects, features and advantages of this invention will become apparent from the following detailed description of the various aspects of the invention taken in conjunction with the accompanying Figures and Examples.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1. Solubilities of UV Absorbers in Various Solvents.

[0012] Figure 2. Color Measurements of Compounds in Polypropylene: Certain

UV absorbers were formulated at a 0.15% level in polypropylene (Profax 6301) and then pelletized using a PL-2000 extruder. The pellets were then injection molded into discs and the discs mounted into cardboard frames. [0013] Figure 3. UV/Vis Spectra in Polyethyleneterephthalate: The UV absorbers were formulated at a 0.15% level in polyethyleneterephthalate (M&G) and then pelletized using a PL-2000 extruder. Films were then compression molded using a thermal press and mounted in cardboard frames. [0014] Figure 4. UV/Vis Spectra in Toluene (10 ppm): The UV absorbers were dissolved to a 1000 ppm level in toluene in a 1 L flask. 10 mL of this solution was diluted to 1 L and UV/Vis spectra taken. [0015] Figure 5. UV/Vis Spectra in Cellulose Acetate: A stock solution of 20 g of cellulose acetate in 100 rnL of acetone and 10 rnL of Cellosolve was prepared. A 20 mg portion of the UV absorber was dissolved in 5 rnL of acetone (or methylene chloride if solubility in acetone was poor). To the UV absorber solution was added 35 g of the stock cellulose acetate solution and the resulting mixture shaken to ensure dissolution. After dispersal of air bubbles, glass slides were dipped into the solution, and the glass slides air dried for one hour and oven dried at 70 ⁰ C for one hour. The films were peeled from the slides and taped to cardboard mounts. UV curves were then run on the films before exposure in the Weatherometer, and after each 250 hour interval.

DETAILED DESCRIPTION OF THE INVENTION

[0016] As summarized above, the present invention is based in part on dimeric cyanoacrylate compounds that are linked either through the ester alkyl group (Type I) or through the p-hydroxy group (Type II), and that absorb UV rays between 320 nm and 400 nm and have low volatility.

[0017] The invention is also based in part on compositions including a dimeric cyanoacrylate disclosed herein, or mixtures thereof, that can be blended with one or more UV stabilizer compounds.

[0018] Accordingly, the compounds and compositions disclosed herein are useful for methods of stabilizing a material that is capable of degradation due to UV radiation and prolonged exposure to sunlight, thereby reducing and/or preventing degradation of the material and/or degradation of the contents packaged by the material as the case may be. Definitions

[0019] As employed above and throughout the disclosure, the following terms are provided to assist the reader. Unless otherwise defined, all terms of art, notations and other scientific or medical terms or terminology used herein are intended to have the meanings commonly understood by those of skill in the chemical arts. In some cases, terms with commonly understood meanings are defined herein for clarity and/or for ready reference, and the inclusion of such definitions herein should not necessarily be construed to represent a substantial difference over the definition of the term as generally understood in the art unless otherwise indicated. As used herein and in the appended claims, the singular forms include plural referents unless the context clearly dictates otherwise.

[0020] Throughout this specification the terms and substituents retain their definitions. A comprehensive list of abbreviations utilized by organic chemists (i.e. persons of ordinary skill in the art) appears in the first issue of each volume of the Journal of Organic Chemistry. The list, which is typically presented in a table entitled "Standard List of Abbreviations" is incorporated herein by reference.

[0021] Alkyl is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof. Lower alkyl refers to alkyl groups of from 1 to 6 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s-and t-butyl and the like. Preferred alkyl groups are those of C ₃₀ or below. Cycloalkyl is a subset of alkyl and includes cyclic hydrocarbon groups having from 3 to 8 carbon atoms, as well as polycyclic hydrocarbons having 7 to 10 carbon atoms. Examples of cycloalkyl groups include c-propyl, c-butyl, c-pentyl, and the like. Examples of C ₇ to C _1O polycyclic hydrocarbons include ring systems such as norbornyl and adamantyl.

[0022] C ₁ to C ₃₀ hydrocarbon includes alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, aryl and combinations thereof. Examples include phenethyl, cyclohexylmethyl, camphoryl and naphthylethyl. Examples of cycloalkenyls include cyclohexenyl, nobornenyl, and the like.

[0023] Alkoxy or alkoxyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy and the like. Lower-alkoxy refers to groups containing one to four carbons.

[0024] Oxaalkyl refers to alkyl residues in which one or more carbons has been replaced by oxygen. Examples include methoxypropoxy, 3,6,9-trioxadecyl and the like.

[0025] Acyl refers to groups of from 1 to 8 carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent structure through a carbonyl functionality. One or more carbons in the acyl residue may be replaced by nitrogen, oxygen or sulfur as long as the point of attachment to the parent remains at the carbonyl. Examples include acetyl, benzoyl, propionyl, isobutyryl, ^-butoxycarbonyl, benzyloxycarbonyl and the like. Lower-acyl refers to groups containing one to four carbons.

[0026] Aryl and heteroaryl mean a 5- or 6-membered aromatic or heteroaromatic ring containing 0-3 heteroatoms selected from O, N, or S; a bicyclic 9- or 10- membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from O, N, or S; or a tricyclic 13- or 14-membered aromatic or heteroaromatic ring system containing 0-3 heteroatoms selected from O, N, or S. The aromatic 6- to 14-membered carbocyclic rings include, e.g., benzene, naphthalene, indane, tetralin, and fluorene and the 5- to 10-membered aromatic heterocyclic rings include, e.g., imidazole, pyridine, indole, thiophene, benzopyranone, thiazole, furan, benzimidazole, quinoline, isoquinoline, quinoxaline, pyrimidine, pyrazine, tetrazole and pyrazole.

[0027] Arylalkyl means an alkyl residue attached to an aryl ring. Examples are benzyl, phenethyl and the like. Fused cycloalkylaryl refers to a cycloalkyl residue fused to an aryl ring. Examples are indane and tetrahydronapthalene.

[0028] Heteroarylalkyl means an alkyl residue attached to a heteroaryl ring.

Examples include, e.g., pyridinylmethyl, pyrimidinylethyl and the like.

[0029] Heterocycle means a cycloalkyl or aryl residue in which from one to three carbons is replaced by a heteroatom selected from the group consisting of N, O and S. The nitrogen and sulfur heteroatoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quaternized. Examples of heterocycles that fall within the scope of the invention include pyrrolidine, pyrazole, pyrrole, indole, quinoline, isoquinoline, tetrahydroisoquinoline, benzofuran, benzodioxan, benzodioxole (commonly referred to as methylenedioxyphenyl, when occurring as a substituent), tetrazole, morpholine, thiazole, pyridine, pyridazine, pyrimidine, thiophene, furan, oxazole, oxazoline, isoxazole, dioxane, tetrahydrofuran and the like. It is to be noted that heteroaryl is a subset of heterocycle in which the heterocycle is aromatic. Examples of heterocyclyl residues additionally include piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxo-pyrrolidinyl, 2-oxoazepinyl, azepinyl, 4-piperidinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazinyl, oxazolidinyl, isoxazolidinyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, tetrahydrofuryl, tetrahydropyranyl, thienyl, benzothienyl, thiamorpholinyl, thiamorpholinylsulfoxide, thiamorpholinylsulfone, oxadiazolyl, triazolyl and tetrahydroquinolinyl. [0030] Substituted alkyl, aryl, cycloalkyl, heterocyclyl, etc. refer to alkyl, aryl, cycloalkyl, or heterocyclyl wherein up to three H atoms in each residue are replaced with halogen, haloalkyl, hydroxy, loweralkoxy, carboxy, carboalkoxy (also referred to as alkoxycarbonyl), carboxamido (also referred to as alkylaminocarbonyl), cyano, carbonyl, nitro, amino, alkylamino, dialkylamino, mercapto, alkylthio, sulfoxide, sulfone, acylamino, amidino, phenyl, benzyl, halobenzyl, heteroaryl, phenoxy, benzyloxy, heteroaryloxy, benzoyl, halobenzoyl, or loweralkylhydroxy.

[0031] The term "halogen" means fluorine, chlorine, bromine or iodine.

[0032] As used herein, and as would be understood by the person of skill in the art, the recitation of "a compound" is intended to include salts, solvates, co-crystals and inclusion complexes of that compound.

[0033] Compounds described herein may contain one or more asymmetric centers and may thus give rise to enantiomers, diastereomers, and other stereoisomeric forms that may be defined, in terms of absolute stereochemistry, as (R)- or (S)-. The present invention is meant to include all such possible isomers, as well as their racemic and optically pure forms and mixtures thereof in any range or proportion. Optically active (R)- and (S)- forms may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. The configuration of any carbon-carbon double bond appearing herein is selected for convenience only and is not intended to designate a particular configuration; thus a carbon-carbon double bond depicted arbitrarily herein as trans may be cis, trans, or a mixture of the two in any proportion. Likewise, all polymorphs and tautomeric forms are also intended to be included. Compounds and Compositions

[0034] In one aspect, the invention provides dimeric cyanoacrylate compounds represented by Formula (I) or Formula (II):

wherein

R ¹ and R ² are independently chosen from hydrogen, C ₁ -C _3O alkyl, and -(CH2) _q -C(O)-OR ⁹ , wherein R ⁹ is chosen from hydrogen and C ₁ -C ₃ O alkyl optionally interrupted with oxygen, provided no oxygen atom is adjacent to another, and wherein q is an integer from 1 to 20;

R ³ and R ⁴ are independently chosen from hydrogen and C ₁ -C ₆ alkoxy;

R ⁵ and R ⁶ are independently chosen from C ₁ -C ₃ O alkyl, and

-(CH ₂ CH ₂ O) _m -(CH ₂ ) _n -CH ₃ , wherein m is an integer from 1 to 20, and n is an integer from 0 to 20;

R ⁷ and R ⁸ are independently chosen from R ³ and R ⁴ ; and

X ¹ and X ² are independently chosen from C ₂ -C _3O alkylene and -( CH ₂ CH ₂ O) _P -CH ₂ CH ₂ -, wherein p is an integer from 1 to 20.

[0035] In some embodiments, the compounds are of Formula (I) and are represented by the following subgenus:

and

wherein p = 1-5.

[0036] In one embodiment, a compound of Formula (I) is represented by

[0037] In another embodiment, a compound of Formula (I) is represented by

[0038] In certain embodiments, compounds of Formula (I) are provided wherein at least one of R ¹ and R ² is -(CH ₂ ) _q -C(O)-OR ⁹ . In a specific embodiment, the compound of Formula (I) having at least one of R ¹ and R ² as -(CH ₂ ) _q -C(O)-OR ⁹ includes:

[0039] In another specific embodiment, the compound of Formula (I) having at least one of R ¹ and R ² as -(CH ₂ ) _q -C(O)-OR ⁹ includes:

[0040] In still another specific embodiment, the compound of Formula (I) having at least one of R ¹ and R ² as -(CH ₂ ) _q -C(O)-OR ⁹ includes:

[0041] In other embodiments, the compounds are of Formula (II) and are represented by the following subgenus:

(Ha) and

(lib) wherein m = 1-5 and n = 0-3.

[0042] In one embodiment, a compounds of Formula (II) is represented by:

(lie).

[0043] In another aspect, the invention provides compositions including mixtures of dimeric cyanoacrylate compounds represented by Formula (I) and/or Formula (II).

[0044] In one embodiment, the composition includes two or more dimeric cyanoacrylate compounds of Formula (I). In certain embodiments when the composition includes two or more dimeric cyanoacrylate compounds of Formula (I), both R ¹ and R ² of said two or more compounds are methoxy, at least one of R ³ and R ⁴ of one compound is hydrogen, and at least one of R ³ and R ⁴ of another compound is methoxy.

[0045] In other embodiments when the composition includes two or more dimeric cyanoacrylate compounds of Formula (I), both R ¹ and R ² of one compound are methoxy, both R ¹ and R ² of a second compound are -(CH ₂ ) _q -C(O)-OR ⁹ , and one of R ¹ or R ² of a third compound is methoxy and the other of R ¹ or R ² is -(CH ₂ ) _q -C(O)-OR ⁹ . A specific embodiment of a composition that includes two or more dimeric cyanoacrylate compounds of Formula (I) includes, but is not limited to, compounds of Formulas (Ic), (Ie), and (If).

[0046] In certain embodiments, X ¹ of these compositions is -(CH ₂ CH ₂ O) _p -

CH ₂ CH ₂ -, wherein p is an integer from 1 to 5.

[0047] In other embodiments, the composition includes two or more dimeric cyanoacrylate compounds of Formula (II). In certain embodiments when the composition includes two or more dimeric cyanoacrylate compounds of Formula (II), at least one of R ⁷ and R ⁸ of one compound is hydrogen and at least one of R ⁷ and R ⁸ of another compound is methoxy.

[0048] In certain embodiments, X2 of these compositions is X is C ₂ -C ₁₂ alkylene and R ⁵ and R ⁶ are -(CH ₂ CH ₂ O) _m -(CH ₂ ) _n -CH ₃ , wherein m is an integer from 1 to 5, and n is an integer from 0 to 3.

[0049] In still other embodiments, the composition includes two or more dimeric cyanoacrylate compounds of Formula (I) and Formula (II). UV Stabilizers and Absorbers

[0050] In still another aspect, the invention provides dimeric cyanoacrylate compounds, or compositions thereof, compounded with one or more UV stabilizer or UV absorber. Such UV stabilizer and absorbers are well known to those of ordinary skill in the art and include, but are not limited to, benzophenones, benzotriazoles, triazine-benzotriazole hybrid UV absorbers, triazine-benzophenone hybrid UV absorbers, benzoxazinones, cyanoacrylates, triazine UV absorbers, hindered amine light stabilizers, antioxidants, and hindered benzoates. The amount of additional UV stabilizer and/or UV absorber to add to the compounds and compositions described herein can be readily determined by one of ordinary skill in the art with the aid of routine technique and/or by consulting textual and/or prior art references.

[0051] Suitable benzophenones for use as additives with the compounds and compositions of the present invention include, but are not limited to, those described in U.S. Patent No. 6,537,670. In certain embodiments, the benzophenone is chosen from a 2-hydroxybenzophenone.

[0052] Suitable benzotriazoles for use as an additive with the compounds and compositions of the present invention include, but are not limited to, 2-(2'-hydroxy-5'- methylphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2- (5'-tert-butyl-2'-hydroxyphenyl)benzotriazole; 2-(2'-hydroxy-5'-(l,3,3- tetramethylbutyl)phenyl)benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5- chlorobenzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro- benzotriazole; 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazol e; 2-(2'- hydroxy-4'-octoxyphenyl)benzotriazole; 2-(3',5'-di-tert-amyl-2'- hydroxphenyl)benzotriazole; 2-(3',5'-bis(. alpha., .alpha.-dimethylbenzyl)-2'- hydroxyphenyl)-benzotriazole; a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2- octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)- 5-chloro-benzotriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro -benzotriazole, 2-(3'- tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benz otriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotri azole, 2-(3'-tert-butyl- 5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzo triazole, 2-(3'-dodecyl- 2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)phenylbenzotriazole; 2,2-methylenebis[4-(l,3,3- tetramethylbutyl)-6-benzotriazol-2-ylphenol], and the transesterification product of 2- [3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300.

[0053] Related triazine-benzotriazole and triazine-benzophenone hybrid UV absorbers are disclosed in U.S. Pat. No. 5,585,422 which is incorporated by reference herein for all purposes fully set forth.

[0054] Suitable benzoxazinones for use as an additive with the compounds and compositions of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 4,446,262, U.S. Pat. No. 5,264,539, and U.S. Patent No. 6,774,232. Specific examples can include, but are not limited to, 2-Methyl-3,l-benzoxazin-4-one, 2-butyl-3,l-benzoxazin-4-one, 2-phenyl-3,l-benzoxazin-4-one, 2-(l- or 2-naphthyl)- 3 , 1 -benzoxazin-4-one, 2- (4-biphenyl)-3 , 1 -benzoxazin-4-one, 2-p-nitrophenyl-3 , 1 - benzoxazin-4-one, 2-m-nitrophenyl-3,l -benzoxazin-4-one, 2-p-benzoylphenyl-3,l- benzoxazin-4-one, 2-p-methoxyphenyl-3,l-benzoxazin-4-one, 2-O-methoxyphenyl- 3,1 -benzoxazin-4-one, 2-cyclohexyl-3,l -benzoxazin-4-one, 2-p-(or m- )phthalimidephenyl-3,l-benzoxazin-4-one, N-phenyl -4-(3,l-benzoxazin-4-one-2- yl)phthalimide, N-benzoyl-4-(3,l-benzoxazine-4-one-2-yl)aniline, N-benzoyl-N- methyl-4-(3,l-benzoxazin-4-one-2-yl)-aniline, 2-[p-(N-phenylcarbamonyl)phenyl]- 3,1 -benzoxazin-4-one, and 2- [p- (N-phenyl N-methylcarbamoyl)phenyl]-3,l- benzoxazin-4-one. 2,2'-bis(3,l-benzoxazin-4-one), 2,2'-ethylenebis(3,l-benzoxazin-4- one), 2,2'-tetramethylenebis(3,l-benzoxazin-4-one), 2,2'-hexamethylenebis(3,l- benzoxazin-4-one), 2,2'-decamethylenebis(3, l-benzoxazin-4-one), 2,2'-p- phenylenebis(3,l-benzoxazin-4-one), 2,2'-m-phenylenebis(3, l-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3, l-benzoxazin-4-one), 2,2'-(2,6-or 1,5- naphthalene)bis(3, l-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3, 1- benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3, l-benzoxazin-4-one), 2,2'-(2- chloro-p-phenylene)bis (3 , 1 -benzoxazin-4-one) , 2,2'- ( 1 ,4-cyclohexylene)bis(3 , 1 - benzoxazin-4-one), N-p-(3,l-benzoxazin-4-on-2-yl)phenyl, 4-(3,l-benzoxazin-4-on- 2-yl)phthalimide, and N-p-(3,l-benzoxazin-4-on-2-yl)benzoyl, 4-(3,l-benzoxazin-4- on-2-yl)aniline, l,3,5-tri(3,l-benzoxazin-4-on-2-yl)benzene, l,3,5-tri(3,l-benzoxazin- 4-on-2-yl)naphthalene, and 2,4,6-tri(3, l-benzoxazin-4-on-2-yl)naphthalene.

[0055] Suitable cyanoacrylates for use as an additive with the compounds and compositions of the present invention include, but are not limited to, those disclosed in U.S. Pat. No. 4,129,667, and U.S. Patent No. 4,410,594.

[0056] Suitable triazine UV absorbers for use as an additive with the compounds and compositions of the present invention include, but are not limited to, 2,4,6-tris(2- hydroxy-4-octyloxyphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-n-octyloxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-mixed iso-octyloxyphenyl)- 4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4- dimethylphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)- 1 ,3,5-triazine; 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3- butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-l,3,5- triazine; 2-[2-hydroxy- 4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy lphenyl)- 1,3,5- triazine; 2- [4-dodecyloxy/tridecyloxy-2-hydroxypropoxy] -2-hydroxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazine; 2-[2-hydroxy-4-(2-hydroxy-3- dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-l,3,5- triazine; 2-(4- methoxyphenyl)-4,6-bis(2-hydroxy-4(2-ethylhexyloxy)phenyl)-l ,3,5-triazine; 2-(2- hydroxy-4-octyloxyphenyl)-4,6-(3,4-dimethylphenyl)-l,3,5-tri azine; 2-(2-hydroxy-4- hexyloxy)phenyl)-4,6-diphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-methoxyphenyl)-4,6- diphenyl)-l,3,5-triazine; 2,4,6-tris[2-hydroxy-4-(3-butoxy-2- hydroxypropoxy)phenyl] -1,3,5 -triazine ; 2- (2-hydroxyphenyl-4- (4-methoxyphenyl) - 6- phenyl- 1,3,5-triazine; 2-[4-(2-ethylhexyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine, as well as those disclosed in U.S. Patent Nos. 6,867,250; 6,855,269; 6,843,939; 6,800,757; and 6,348,591 and other commercially available triazine UV absorbers. 57] Suitable hindered amine light stabilizers for use as an additive with the compounds and compositions of the present invention include, but are not limited to, 2,2,6,6-tetramethyl-4-piperidyl laurate; 2,2,6,6-tetramethyl-4-piperidyl myristate; 2,2,6,6-tetramethyl-4-piperidyl palmitate; 2,2,6, 6-tetramethyl-4-piperidyl stearate; 2,2,6,6-tetramethyl-4-piperidyl oleate; 2,2,6, 6-tetramethyl-4-piperidyl 12- hydroxystearate; 2,2,6, 6-tetramethyl-4-piperidyl behenate; 2,2,6, 6-tetramethyl-4- piperidyl heptadecanoate; l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl stearate; 1- cyclohexyloxyl-2,2,6,6-tetramethyl-4-piperidyl stearate; 2-hydroxy-2-methylpropoxy- 2,2,6,6-tetramethyl-4-piperidyl stearate; l-(4-octadecanoyloxy-2,2,6,6- tetramethylpiperidin-l-yloxy)-2-octadecanoyloxy-2-methylprop ane; 1,2,2,6,6- pentamethyl-4-piperidyl stearate; l-acetyl-2,2,6,6-tetramethyl-4-piperidyl stearate; and l-oxy-2,2,6,6-tetramethyl-4-piperidyl stearate, sterically hindered amines as well as the N derivatives thereof (e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidin-4- yl)succinate; bis(l, 2,2,6, 6-pentamethylpiperidin-4-yl)sebacate; bis(l-octyloxy- 2,2,6,6-tetramethylpiperidin-4-yl)sebacate; bis(l, 2,2,6, 6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4-hydroxybenzylmalonate; the condensate of l-(2- hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; the condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediam ine and 4-tert-octylamino-2,6-dichloro- 1 ,3,5-triazine; tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)- 1 ,2,3,4- butanetetracarboxylate ; l,l'-(l,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4- benzoyl-2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis(l, 2,2,6, 6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-b ut ylbenzyl)malonate; 3-n-octyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decan-2, 4- dione; bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate; bis(l-octyloxy-2,2,6,6- tetramethylpiperidyl)succinate; the condensate of N,N-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro- 1,3, 5 -triazine; the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6- tetramethylpiperidyl)-l,3,5-triazi ne and l,2-bis(3-aminopropylamino)ethane; the condensate of 2-chloro-4,6-bis(4-n-butylamino- 1,2,2,6,6-pentamethylpiperidyl)- 1,3,5- tria zine and l,2-bis-(3-aminopropylamino)ethane; 8-acetyl-3-dodecyl-7,7,9,9- tetramethyl-l,3,8-triazaspiro[4. 5]decane-2,4-dione; 3-dodecyl-l -(2,2,6,6- tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione; 3-dodecyl-l-(l-ethanoyl-2,2,6,6- tetramethylpiperidin-4-yl)pyrrolidin-2,5-d ione; 3-dodecyl-l -(1,2,2,6,6- pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; a mixture of 4-hexadecyloxy- and A- stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate of N,N'-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6- dichloro-l,3,5-triazine; the condensate of l,2-bis(3-aminopropylamino)ethane, 2,4,6- trichloro-l,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); 2-undecyl-7,7,9,9-tetramethyl-l-oxa-3,8-diaza-4- oxospiro[4.5]decane; oxo-piperanzinyl-triazines or so-called PIP-T HALS, e.g., GOODRITE® 3034, 3150 and 3159 and similar materials disclosed in U.S. Pat. No. 5,071,981; photobondable HALS such as SANDUVOR® PR-31 and PR-32 (Clariant Corp.) and similar materials disclosed in GB-A-2269819; and the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospir o[4.5]decane and epichlorohydrin, as well as the hindered amine compounds disclosed in U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,106,891, U.S. Pat. No. 6,843,939, GB-A-2269819, EP-A- 0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608, and other commercially available triazine UV absorbers. 58] Suitable antioxidants for use as an additive with the compounds and compositions of the present invention include, but are not limited to, phenolic antioxidants in which the phenolic hydroxyl group is flanked by alkyl or arylalkyl groups and phosphite antioxidants. Phenolic antioxidants can be based on, for example, structures similar to 2,6-di-t-butyl-4-methylphenol (BHT), in which t-butyl groups symmetrically flank the phenolic hydroxyl group. Phosphite antioxidants can include, but are not limited to, (bis-(2,4-dicumylphenyl)pentaerythritol diphosphite (DOVERPHOS® S-9228) and tris-(2,4-di-t-butylphenyl) phosphite (IRGANOX® 168). A blend containing 64.1% CYASORB® UV-3529 (l,6-hexanediamine,N,N'- bis(l,2,2,6,6-pentamethyl)-4-piperidinyl)-, polymers with 2,4-dichloro-6-(4- morpholinyl)-l,3,5-triazine), 7.7 % CYANOX® 1790 (l,3,5-tris(4-t-butyl-3- hydroxy-2,6-dimethyl benzyl)- l,3,5-triazine-2,4,6-(lH,3H,5H)-trione), 14.5% IRGAPHOS® 168 (tris-(2,4-di-t-butylphenyl)phosphite), 7.7% ULTRANOX® 626 (bis-(2,4-di-t-butylphenyl) pentaerythritol diphosphite) and 5.1% KADOX® 911 (Zinc Oxide). Other antioxidants suitable for use with the compounds and compositions of the present invention also include those disclosed in WO2007/136565.

[0059] Suitable hindered benzoates for use as an additive with the compounds and compositions of the present invention include, but are not limited to, those disclosed in U.S. Patent No. 6,843,939. For example, the hindered benzoate can include any of, but is not limited to, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl-3,5-di-tert-butyl-4- hydroxybenzoate; octyl-3,5-di-tert-butyl-4-hydroxybenzoate; tetradecyl-3,5-di-tert- butyl-4-hydroxybenzoate; behenylyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-methyl- 4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and butyl 3-[3-t-butyl-4- (3,5-di-t-butyl-4-hydroxybenzoyloxy)phenyl]propionate. Methods

[0060] In another aspect, the invention provides methods for stabilizing a material that is subject to degradation by UV radiation by incorporating a compound or composition described herein into the material. In one embodiment, the incorporating step is performed physically as by blending or compounding. In another embodiment, the incorporating step can be performed chemically.

[0061] In one embodiment, the material in which the compounds and compositions of the present invention are incorporated is a polymeric material that can be chosen from any of, for example, polyolefins; polyesters; polyethers; polyketones; polyamides; natural and synthetic rubbers; polyurethanes; polystyrenes; high-impact polystyrenes; polyacrylates; polymethacrylates; polyacetals; polyacrylonitriles; polybutadienes; polystyrenes; ABS; styrene acrylonitrile;acrylate styrene acrylonitrile; cellulosic acetate butyrate; cellulosic polymers; polyimides; polyamideimides; polyetherimides; polyphenylsulfides; polyphenylene oxide; polysulfones; polyethersulfones; polyvinylchlorides; polycarbonates; polyketones; aliphatic polyketones; thermoplastic TPOs; aminoresincrossliked polyacrylates and polyesters; polyisocyante crosslinked polyesters and polyacrtlates; phenol/formaldehyde resins; urea/formaldehyde resins; melamine/formaldehyde resins; drying and non-drying alkyd resins; alkyd resins; polyester resins; acrylate resins crosslinked with melamine resins; urea resins; isocyanates; isocyanurates; carbamates; epoxy resins; crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic, and aromatic glycidyl compounds that are crosslinked with anhydrides or amines; polysiloxanes; Michael addition polymers; amines; blocked amines with activated unsaturated and methylene compounds; ketimines with activated unsaturated and methylene compounds; polyketimines in combination with unsaturated acrylic resins; radiation curable compositions; epoxymelamine resins; organic dyes; cosmetic products; cellulose-based paper formulations; photographic film paper; ink; waxes; and fibers.

[0062] In an embodiment, the material can be a polyolefin that includes, but is not limited to, polyethylene; high polyethylene; low density polyethylene; low density polyethylene/EVA copolymers; linear low density polyethylene; metallocene polyethylene; crosslinked polyethylene; polypropylene rubber-modified polypropylene; and other copolymers and blends thereof.

[0063] In an embodiment, the stabilizing amount of the compound or composition to be added to the material ranges from 0.05% to 30% by weight of the material to be stabilized.

Examples

[0064] The following examples are provided to assist one skilled in the art to further understand embodiments of the present invention. These examples are intended for illustration purposes but are not to be construed as limiting the scope of the embodiments of the present invention.

[0065] Generalized synthetic schemes showing the various interrelated processes of the invention are presented below as Examples 1-X. In general, the compounds of the present invention may be prepared by the methods illustrated in the general reaction schemes as, for example, described below, or by modifications thereof, using readily available starting materials, reagents and conventional synthesis procedures. In these reactions, it is also possible to make use of variants that are in themselves known, but are not mentioned here. Thus, chemical compounds utilized in these examples (summarized below) are obtained from commercial sources or prepared by known methods:

Syntheses of Compounds:

[0066] Example 1

(Hc)

[0067] Step I Preparation of Dimeric Aldehyde

To a 1 L 3-necked round bottomed flask equipped with a condenser, mechanical stirrer, and thermometer was charged 119.1 g (0.78 mol) of vanillin, 84.2 g (0.39 mol) of dibromobutane, and 600 mL of a solution of 31.2 g (0.78 mol) of sodium hydroxide in water. The mixture was heated to reflux. After refluxing for 17 hours, the solution was cooled and the solid filtered and washed with water. Recrysallization from acetonitrile (600 g) gave 89 g of a tan solid. [0068] Step II Preparation of diethylene glycol ethyl ether cyanoacetate

To a stirring mixture of diethylene glycol monoethyl ether (268 g, 2.0 mol), cyanoacetic acid (175 g, 2.05 mol) and 1250 mL toluene in a 2 L four-neck round bottom flask equipped with an overhead stirrer, a nitrogen inlet, a Dean-Stark apparatus with a water condenser and a thermometer is added 25 g of p-toluenesulfonic acid (p-TSA) at room temperature. The mixture is refluxed while water is collected as a toluene azeotrope. A total of about 32 mL of water is collected. The mixture is stripped to remove toluene and the residue diluted with 500 mL methylene chloride. The precipitated p-TSA is filtered. The filtrate is diluted with another 500 mL methylene chloride, washed with water to neutral pH, and then stripped to dryness to give 390 g of the crude dimeric cyanoacrylate. Fractional distillation is performed at reduced pressure to give the final product, structure as shown above.

[0069] Step III Reaction of Diethylene Glycol Ethyl Ether Cyanoacetate with

Dimeric Aldehyde (Preparation of Cyanoacrylate Compound 1).

To a 4 L round-bottomed flask equipped with a magnetic stirrer and nitrogen inlet/outlet, was charged 82.3 g (0.41 mol) of diethylene glycol ethyl ether cyanoacetate, 73.2 g (0.204 mol) of the dimeric aldehyde, and 2100 mL of dimethyl formamide. To this stirring suspension was added 15.1 g (0.25 mol) of acetic acid, followed by 18.9 g (0.225 mol) of piperidine. The mixture was allowed to stir for 17 hours, then was diluted with 300 mL of water, filtered, and the filter cake washed with water. The solid was dissolved in methylene chloride and the organic solution washed with 4 x 100 niL of water. After drying (MgSO ₄ ) of the organic layer, and filtration, the filtrate was rotary evaporated, giving 126.9 g of a yellow solid. Recrystallization from 30% ethyl acetate/acetonitrile gave 113.3 g of the pure material as a yellow solid, with melting point (DSC onset) of 132 ⁰ C. [0070] Example 2

Preparation of 3-methoxy-4-(2-ethoxy-2-oxoethoxy)benzaldehyde from Vanillin

To a 5L four- neck, round bottom flask, was charged 20Og vanillin, 112g ethyl chloroacetate, 40Og potassium carbonate, 1Og potassium iodide, 5g Alliquat-336 and 2L MIBK. The reaction mixture was heated to reflux temperature for 4 hrs using an oil- bath. The heating was discontinued and the reaction mixture cooled to room temperature, and then diluted with water. The organic layer was separated and washed twice with water. The solvent from the organic layer was removed under reduced pressure. The residue thus obtained was dried in a vacuum oven at 70 deg C overnight to obtain 187g of the desired product characterized by NMR, LC/MS as 3-methoxy-4-(2-ethoxy-2- oxoethoxy)benzaldehyde. [0071] Example 3

[0072] Step I Synthesis of Diethylene Glycol Bis(Cyanoacrylate):

To a stirring mixture of diethylene glycol (106 g, 1.0 mol), cyanoacetic acid ( 175 g, 2.05 mol) and 1250 mL toluene in a 2 L four-neck round bottom flask equipped with an overhead stirrer, a nitrogen inlet, a Dean- Stark apparatus with a water condenser and a thermometer is added 25 g of p-toluenesulfonic acid (p-TSA) at room temperature. The mixture is refluxed while water is collected as a toluene azeotrope. A total of about 32 niL of water is collected. The mixture is stripped to remove toluene and the residue diluted with 500 mL methylene chloride. The precipitated p-TSA is filtered. The filtrate is diluted with another 500 mL methylene chloride, washed with water to neutral pH, and then stripped to dryness to give 205 g of the crude dimeric cyanoacrylate. Fractional distillation is performed at reduced pressure to give the final product, structure as shown above. [0073] Step II (Preparation of Cyanoacrylate Compound 2)

To a stirring mixture of diethylene glycol based dimeric cyanoacrylate ( 100 g; 0.42 M), (140 g; 0.84 M) and 1000 mL DMF in a 2 L four-neck round bottom flask equipped with an overhead stirrer, a nitrogen inlet, a Dean-Stark apparatus with a water condenser and a thermometer is added 40 g of acetic acid (0.67 M) followed by 32 g of piperidine (0.38 M) at 3-5 ⁰ C. The mixture is allowed to warm to room temperature after Vi h, and then continued to stir at room temperature for about 6 h. The reaction is monitored by HPLC for the disappearance of the 3,4-dimethoxybenzaldehyde. The solvent DMF is then stripped at reduced pressure along with acetic acid and piperidine. To the residue are added 1500 mL methanol and 50 mL acetic acid and the resulting mixture stirred at room temperature for 2-4 h. The material is then filtered, and washed with methanol (2x500 mL). The product P-4342 is then dried in a vacuum oven at 20 ⁰ C. The heat is gradually raised to 60 ⁰ C over several hours. Isolated yield of the product is about 200 g. [0074] Example 4

[0075] Step I Preparation of of Triethylene Glycol Bis(Cyanoacrylate):

The procedure described in Example 2, Step I was repeated, using triethylene glycol (150 g, 1.0 mol) and cyanoacetic acid (175 g, 2.05 mol) to give the pure dimeric cyanoacrylate after vacuum distillation. [0076] Step II Preparation of Cyanoacrylate To a 4 L round-bottomed flask equipped with a magnetic stirrer and nitrogen inlet/outlet, was charged 93.7 g (0.33 mol) of triethylene glycol bis(cyanoacetate), 109.5 g (0.66 mol) of the dimethoxybenzaldehyde, and 1800 mL of dimethylformamide. To this stirring suspension was added 21.0 g (0.35 mol) of acetic acid, followed by 26.4 g (0.31 mol) of piperidine. The mixture was allowed to stir for 17 hours, then was diluted with 300 mL of water, filtered and the filter cake washed with water. The solid was reslurried in methanol, then was refiltered. Recrystallization from toluene, then 2-butanone gave 65 g of product as a light yellow solid, with melting point (DSC onset) of 146 ⁰ C. [0077] Example 5

Preparation of Compound (Ie)

+ NCCH ₂ COO ^' OCOCH ₂ CN piperidine; acetic acid DMF

(Ie).

To a stirring mixture of 12.5 g of diethylene glycol based dimeric cyanoacetate as shown above, 24.0 g of 3-methoxy-4-(2-ethoxy-2-oxoethoxy)benzaldehyde and 250 mL DMF in a 500 mL four-neck round bottom flask equipped with an overhead stirrer, a nitrogen inlet, a water condenser and a thermometer is added 5 g of acetic acid followed by 3.2 g of piperidine at 3-5 ⁰ C. The mixture is allowed to warm to room temperature after Vi h, and then continued to stir at room temperature for about 12 h. The DMF solvent along with acetic acid and piperidine is then stripped under reduced pressure. To the residue is added 175 rnL methanol and 3.5 rnL acetic acid and stirred at room temperature for 2-4 h. The material is then filtered, and washed with methanol. The resulting product is then dried in a vacuum oven first at 20 ⁰ C and then gradually raised to 60 ⁰ C for several hours. The 24 g of the product thus obtained is analyzed by LCMS to contain compound (Ie) as the main product. [0078] Example 6

Preparation of Compounds (Ic), (Ie) and (If)

To a stirring mixture of 12.0 g of diethylene glycol based dimeric cyanoacetate, 12.0 g of 3-methoxy-4-(2-ethoxy-2-oxoethoxy)benzaldehyde, 8.3 g of 3,4-dimethoxybenzaldehyde in 150 mL DMF in a 500 mL four-neck round bottom flask equipped with an overhead stirrer, a nitrogen inlet, a water condenser and a thermometer is added 6 g of acetic acid followed by 4.5 g of piperidine at 3-5 ⁰ C. The mixture is allowed to warm to room temperature after Vi h, and then continued to stir at room temperature for about 12 h. The DMF solvent is then stripped at reduced pressure along with acetic acid and piperidine. To the residue is added 150 rnL methanol and stirred at room temperature for 2-4 h. The material is then filtered, and washed with methanol. The resulting product is then dried in a vacuum oven first at 20 ⁰ C and then gradually raised to 60 ⁰ C for several hours. The product is analyzed by LCMS to contain the three dimeric cyanoacrylates (Ic), (Ie), and

(if).

[0079] Example 7

Preparation of Compounds (Ia), (Ie) and (Ig)

To a stirring mixture of 12.0 g of diethylene glycol based dimeric cyanoacetate, 12.0 g of 3-methoxy-4-(2-ethoxy-2-oxoethoxy)benzaldehyde, 7 g of 4-methoxybenzaldehyde in 150 mL DMF in a 500 mL four-neck round bottom flask equipped with an overhead stirrer, a nitrogen inlet, a water condenser and a thermometer is added 6 g of acetic acid followed by 4.5 g of piperidine at 3-5 ⁰ C. The mixture is allowed to warm to room temperature after ¹ A h, and then continued to stir at room temperature for about 12 h. The DMF solvent is then stripped at reduced pressure along with acetic acid and piperidine. To the residue is added 150 mL methanol and stirred at room temperature for 2-4 h. The material is then filtered, and washed with methanol. The resulting product is then dried in a vacuum oven first at 20 ⁰ C and then gradually raised to 60 ⁰ C for several hours. The product is analyzed by LCMS to contain a mixture of three dimeric cyanoacrylates (Ia), (Ie) and (Ig).

[0080] Various patent and/or scientific literature references have been referred to throughout this application. The disclosures of these publications in their entireties are hereby incorporated by reference as if written herein. In view of the above description and the examples, one of ordinary skill in the art will be able to practice the disclosure as claimed without undue experimentation.

[0081] Although the foregoing description has shown, described, and pointed out the fundamental novel features of the present teachings, it will be understood that various omissions, substitutions, and changes in the form of the detail of the apparatus as illustrated, as well as the uses thereof, may be made by those skilled in the art, without departing from the scope of the present teachings. Consequently, the scope of the present teachings should not be limited to the foregoing discussion, but should be defined by the appended claims.